CN108978341B - Paper flame retardant with good film forming performance and preparation method thereof - Google Patents
Paper flame retardant with good film forming performance and preparation method thereof Download PDFInfo
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- CN108978341B CN108978341B CN201810791069.9A CN201810791069A CN108978341B CN 108978341 B CN108978341 B CN 108978341B CN 201810791069 A CN201810791069 A CN 201810791069A CN 108978341 B CN108978341 B CN 108978341B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention discloses a paper flame retardant with good film forming property and a preparation method thereof, and solves the problems of uneven distribution of flame retardants, poor film forming property and easy aging and fracture in the prior art. The invention relates to a paper flame retardant with good film-forming property, which comprises the following raw materials in parts by weight: 10-30 parts of ammonium polyphosphate, 40-100 parts of decabromodiphenylethane and 500 parts of modified vinyl acetate copolymer emulsion. The preparation method comprises the following steps: taking the modified vinyl acetate copolymer emulsion as a dispersion, adding other raw materials, uniformly mixing, and discharging. The paper flame retardant has good film forming performance, can ensure that the flame retardant is uniformly distributed, has good mechanical property, and is not easy to age and break.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a paper flame retardant with good film forming performance and a preparation method thereof.
Background
The paper is made of fibers which are interwoven, so that the paper is flammable, has high burning speed and forms a fire which develops rapidly. The flame retardancy of paper is required in some special industries. The preparation of paper with flame-retardant effect is generally examined in the following respects: firstly, if the raw materials are prepared by adopting the flame-retardant fibers, the burning of the paper can be stopped from the source, but the cost of the paper prepared by the method is very high; secondly, to isolate the paper from the flame, or to reduce the oxygen content and the combustion temperature, this method generally employs the addition of flame retardants.
There are 3 methods for preparing flame-retardant paperboard by using flame retardant: the first coating method is to coat the fire retardant on the surface of the paper; the second is a dipping method, dipping the paper into the solution containing the flame retardant; and thirdly, adding the flame retardant into the pulp during pulping. The paper prepared by the impregnation method has the defect of strong hygroscopicity. The paper prepared by the in-pulp addition method has adverse effects on the performance of the paper. The flame-retardant paperboard is prepared by a coating method, so that the two problems can be effectively avoided. However, when the coating method is adopted, the problems of uneven distribution of the flame retardant, poor film-forming property and easy occurrence of aging and fracture exist.
Therefore, it is an urgent need to solve the problem of the art to provide a flame retardant for paper with good film forming property, which can uniformly distribute the flame retardant, has good mechanical properties, and is not easy to age or break.
Disclosure of Invention
The technical problem solved by the invention is as follows: the paper flame retardant with good film forming property is provided, and the problems of uneven distribution of the flame retardant, poor film forming property and easy aging and fracture in the prior art are solved.
The invention also provides a preparation method of the paper flame retardant with good film-forming property.
The technical scheme adopted by the invention is as follows:
the paper flame retardant with good film-forming property comprises the following raw materials in parts by weight: 10-30 parts of ammonium polyphosphate, 40-100 parts of decabromodiphenylethane and 500 parts of modified vinyl acetate copolymer emulsion.
Further, the modified vinyl acetate copolymer emulsion is prepared from the following components in parts by weight: 100-300 parts of vinyl acetate, 50-80 parts of butyl acrylate, 1-3 parts of polyvinyl alcohol, 1-5 parts of nano silicon dioxide, 0.1-1 part of hydroxypropyl methyl cellulose, 1000 parts of water 400-containing organic solvent, 1-3 parts of emulsifier and 1-3 parts of initiator.
Further, the modified vinyl acetate copolymer emulsion is prepared from the following components in parts by weight: 200 parts of vinyl acetate, 60 parts of butyl acrylate, 2 parts of polyvinyl alcohol, 3 parts of nano silicon dioxide, 0.5 part of hydroxypropyl methyl cellulose, 400 parts of water, 2 parts of emulsifier and 2 parts of initiator.
Further, the emulsion is selected from one or two of OP-10 and sodium dodecyl sulfate.
Further, the mass ratio of the OP-10 to the sodium dodecyl sulfate is 1: 2-5.
Further, the initiator is potassium persulfate.
Further, 10-30 parts of magnesium hydroxide.
The method for preparing the paper flame retardant with good film-forming property comprises the following steps:
step 1, preparing raw materials according to parts by weight;
and 2, taking the modified vinyl acetate copolymer emulsion as a dispersion liquid, adding other raw materials, uniformly mixing, and discharging.
Further, the preparation method of the modified vinyl acetate copolymer emulsion comprises the following steps:
step A, preparing the components in parts by weight;
step B, adding water into the initiator to prepare an initiator solution with the concentration of 5-10 wt%;
c, adding 8-12 times of water into the hydroxypropyl methyl cellulose, performing ultrasonic dispersion uniformly, and then adding the nano silicon dioxide to perform continuous ultrasonic dispersion to obtain liquid A;
and D, adding the rest of water into the polyvinyl alcohol, heating, cooling to 50-60 ℃ after the polyvinyl alcohol is completely dissolved, adding an emulsifier, vinyl acetate and butyl acrylate, emulsifying for 20-40min, adding three-fourths of initiator solution, stirring at 70-80 ℃ for reaction, continuously dropwise adding the rest of initiator solution when no monomer is condensed and refluxed, adding the liquid A prepared in the step C after dropwise adding is finished, keeping the temperature for reaction for 3-4 hours under the stirring condition, cooling to room temperature, and discharging.
The OP-10 is polyoxyethylene ether.
Compared with the prior art, the invention has the following beneficial effects:
the paper flame retardant has good film forming performance, can ensure that the flame retardant is uniformly distributed, has good mechanical property, and is not easy to age and break.
The paper flame retardant with good film-forming property is obtained by mixing ammonium polyphosphate, decabromodiphenylethane and modified vinyl acetate copolymer emulsion. The invention improves the film forming property by carrying out copolymerization modification on the vinyl acetate and the butyl acrylate, and effectively improves the water resistance, the cold resistance and the temperature resistance.
The invention further modifies the vinyl acetate by adding uniformly dispersed hydroxypropyl methyl cellulose and nano silicon dioxide mixed solution. Wherein, the nano silicon dioxide can generate silicon-oxygen bonds with the copolymer thereof, and the film forming property of the copolymer is effectively improved. The hydroxypropyl methyl cellulose is used as a protective colloid and has hydrogen bonds, so that the modified copolymer can be uniformly dispersed, and the ammonium polyphosphate, the decabromodiphenylethane and the magnesium hydroxide added into the vinyl acetate copolymer emulsion can be uniformly dispersed. After the paper coating agent is coated on paper, hydroxypropyl methyl cellulose can be tightly combined with paper fibers, so that the coating effect is enhanced. Meanwhile, the hydroxypropyl methyl cellulose can also enhance the mechanical property of the flame retardant, so that the flame retardant coated on the paper is not easy to break.
Detailed Description
The following embodiments are intended to explain the present invention in more detail, but the scope of the subject matter of the present invention is not limited to the following embodiments, and all the techniques and processes realized based on the present invention are within the scope of the present invention.
The viscosity of the flame retardant in the examples of the present invention was measured at room temperature using a DV-1 digital viscometer. The stability of the flame retardant was observed by leaving the flame retardant for three months. The water absorption of the flame retardant is measured according to GB/T1733-93.
The mechanical property test of the paper flame retardant in the embodiment of the invention is as follows: the prepared paper flame retardant is dried in a vacuum drying oven for 24 hours for later use, the paper flame retardant is punched into dumbbell type standard tensile test sample strips by a cutter, and the tensile property of the sample strips is tested by a CMT4104 microcomputer control electronic universal tester.
The burning test of the paper in the embodiment of the invention is carried out according to GB/T14656-:
the paper was cut into 21cm × 7cm, the flame retardant-containing paper was obtained by a coating method, the flame was ignited with a flame adjusted to a length of 4cm for 12 seconds, and then the flame was removed to measure the ember time and the length of the carbonized strands. Each set of burning tests was performed for 2 times.
The tensile property test of the paper in the embodiment of the invention is carried out according to GB/T12914-2008, which specifically comprises the following steps:
the specimen size was 21cm by 1.5cm, the measuring range was set to 200mm, the drawing rate was 20mm/min, and the nip pitch was set to 180 mm. Tensile properties tests were performed in parallel for 2 experiments.
In the examples, OP-10 is polyoxyethylene ether and the polyvinyl alcohol is polyvinyl alcohol-1799.
Example 1
This example provides a preparation of the modified vinyl acetate copolymer emulsion of the present invention, specifically:
step A, preparing the components in parts by weight: 200 parts of vinyl acetate, 60 parts of butyl acrylate, 2 parts of polyvinyl alcohol, 3 parts of nano silicon dioxide, 0.5 part of hydroxypropyl methyl cellulose, 400 parts of water, 2 parts of OP-10 and sodium dodecyl sulfate (mass ratio is 1: 2) and 2 parts of potassium persulfate.
B, adding water into potassium persulfate to prepare an initiator solution with the concentration of 5 wt%;
c, adding 10 times of water into the hydroxypropyl methyl cellulose, performing ultrasonic dispersion uniformly, and then adding the nano silicon dioxide to perform continuous ultrasonic dispersion to obtain a liquid A;
and D, adding the rest of water into polyvinyl alcohol, heating, cooling to 50-60 ℃ after the polyvinyl alcohol is completely dissolved, adding an emulsifier, vinyl acetate and butyl acrylate, emulsifying for 30min, adding an initiator solution with three quarters of the total amount, stirring for reaction at 70-80 ℃, continuing to dropwise add the rest of the initiator solution when no monomer is condensed and refluxed, adding the liquid A prepared in the step C after dropwise addition, preserving heat for reaction for 3 hours under the stirring condition, cooling to room temperature, and discharging to obtain the modified vinyl acetate copolymer emulsion.
Example 2
This example provides the preparation of a modified vinyl acetate copolymer emulsion of the present invention, differing only in the raw material composition compared to example 1, with the same remaining conditions.
The composition of the raw materials of this example is: 300 parts of vinyl acetate, 50 parts of butyl acrylate, 3 parts of polyvinyl alcohol, 1 part of nano silicon dioxide, 1 part of hydroxypropyl methyl cellulose, 400 parts of water, 3 parts of sodium dodecyl sulfate and 1 part of potassium persulfate.
Example 3
This example provides the preparation of a modified vinyl acetate copolymer emulsion of the present invention, differing only in the raw material composition compared to example 1, with the same remaining conditions.
The composition of the raw materials of this example is: 100 parts of vinyl acetate, 80 parts of butyl acrylate, 1 part of polyvinyl alcohol, 5 parts of nano silicon dioxide, 0.1 part of hydroxypropyl methyl cellulose, 1000 parts of water, OP-101 parts and 3 parts of potassium persulfate.
Example 4
This example provides the preparation of the paper flame retardant of the present invention, specifically as follows:
step 1, preparing raw materials in parts by weight: 400 parts of modified vinyl acetate copolymer emulsion prepared in example 1, 20 parts of ammonium polyphosphate and 60 parts of decabromodiphenylethane;
and 2, sequentially adding ammonium polyphosphate and decabromodiphenylethane into the modified vinyl acetate copolymer emulsion prepared in the example 1, ultrasonically mixing uniformly, and discharging.
Example 5
This example provides a review of the different emulsifiers.
In this example, the kind and amount of the emulsifier were different from those in example 4, and the other conditions were the same. The flame retardant for paper prepared in this example was used to test the viscosity, water absorption and stability, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, OP-10: the mass ratio of the dodecyl sulfuric acid is 1: 2, the flame retardant has the best properties.
Example 6
This example provides a review of the different amounts of hydroxypropyl methylcellulose used.
In this example, the amount of hydroxypropyl methylcellulose used was different for each paper flame retardant than in example 4, and the other conditions were the same. The paper flame retardants obtained in this example were used to test their viscosity, water absorption, stability, and mechanical properties, and the results are shown in table 2.
The paper flame retardants obtained in this example were applied to the same paper in an amount of 60g/m2. The effect of the test on the flame retardant property of paper is shown in Table 3.
TABLE 2
TABLE 3
As is clear from tables 2 and 3, the index was the best when the amount of hydroxypropylmethylcellulose was 0.5 part.
Example 7
This example provides a review of the amount of different nanosilica.
Compared with the flame retardant used in example 4, the flame retardant used in paper in this example has different amounts of nano-silica, and the other conditions are the same. The paper flame retardants obtained in this example were used to test their viscosity, water absorption, stability, and mechanical properties, and the results are shown in table 4.
Get thisThe flame retardants for paper prepared in the examples were coated on the same paper in an amount of 60g/m2. The effect on the flame retardant property of paper was tested and the specific results are shown in table 5.
TABLE 4
TABLE 5
As can be seen from tables 4 and 5, the index was the best when the amount of the nano-silica was 3 parts.
Example 8
This example provides a review of the types and amounts of different materials.
In this example, the kinds and amounts of the raw materials were different from those in example 4, and the other conditions were the same. The paper flame retardants obtained in this example were applied to the same paper in an amount of 60g/m2. The effect on the flame retardant property of paper was tested and the specific results are shown in table 6.
Note: the modified vinyl acetate copolymer emulsions of this example were all the modified vinyl acetate copolymer emulsions prepared in example 1.
As can be seen from the above table, the flame retardant of the present invention has good flame retardant properties.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (5)
1. The flame retardant with good film forming property for paper is characterized by comprising the following raw materials in parts by weight: 10-30 parts of ammonium polyphosphate, 40-100 parts of decabromodiphenylethane and 500 parts of modified vinyl acetate copolymer emulsion;
the modified vinyl acetate copolymer emulsion is prepared from the following components in parts by weight: 100-300 parts of vinyl acetate, 50-80 parts of butyl acrylate, 1-3 parts of polyvinyl alcohol, 1-5 parts of nano silicon dioxide, 0.1-1 part of hydroxypropyl methyl cellulose, 1000 parts of water 400-containing organic solvent, 1-3 parts of emulsifier and 1-3 parts of initiator;
the emulsifier is OP-10 and sodium dodecyl sulfate, and the mass ratio of the OP-10 to the sodium dodecyl sulfate is 1: 2-5;
the preparation method of the modified vinyl acetate copolymer emulsion comprises the following steps:
step A, preparing the components in parts by weight;
step B, adding water into the initiator to prepare an initiator solution with the concentration of 5-10 wt%;
c, adding 8-12 times of water into the hydroxypropyl methyl cellulose, performing ultrasonic dispersion uniformly, and then adding the nano silicon dioxide to perform continuous ultrasonic dispersion to obtain liquid A;
and D, adding the rest of water into the polyvinyl alcohol, heating, cooling to 50-60 ℃ after the polyvinyl alcohol is completely dissolved, adding an emulsifier, vinyl acetate and butyl acrylate, emulsifying for 20-40min, adding three-fourths of initiator solution, stirring at 70-80 ℃ for reaction, continuously dropwise adding the rest of initiator solution when no monomer is condensed and refluxed, adding the liquid A prepared in the step C after dropwise adding is finished, keeping the temperature for reaction for 3-4 hours under the stirring condition, cooling to room temperature, and discharging.
2. The flame retardant for paper with good film-forming property of claim 1, wherein the modified vinyl acetate copolymer emulsion is prepared from the following components in parts by weight: 200 parts of vinyl acetate, 60 parts of butyl acrylate, 2 parts of polyvinyl alcohol, 3 parts of nano silicon dioxide, 0.5 part of hydroxypropyl methyl cellulose, 400 parts of water, 2 parts of emulsifier and 2 parts of initiator.
3. The flame retardant for paper with good film-forming property according to claim 1, wherein the initiator is potassium persulfate.
4. A flame retardant for paper with good film forming property according to any one of claims 1 to 3, characterized by further comprising 10 to 30 parts of magnesium hydroxide.
5. A method for preparing a flame retardant for paper with good film forming property according to any one of claims 1 to 4, characterized by comprising the steps of:
step 1, preparing raw materials according to parts by weight;
and 2, taking the modified vinyl acetate copolymer emulsion as a dispersion liquid, adding other raw materials, uniformly mixing, and discharging.
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| CN201810791069.9A CN108978341B (en) | 2018-07-18 | 2018-07-18 | Paper flame retardant with good film forming performance and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166870A (en) * | 2011-01-05 | 2011-08-31 | 上海奇葩环境科技有限公司 | Method for manufacturing fireproof flame-retardation wallpaper |
| CN105131438A (en) * | 2015-09-02 | 2015-12-09 | 中国化工集团曙光橡胶工业研究设计院有限公司 | High-thermal-insulation ablation-resistant sizing material |
| CN107629736A (en) * | 2017-09-07 | 2018-01-26 | 滁州市光威化工有限公司 | A kind of nano-silicon dioxide modified fire-retardant the High-speed Cigarette Adhesives for Filter Tipping of hud typed acrylate and vinyl acetate emulsion and preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166870A (en) * | 2011-01-05 | 2011-08-31 | 上海奇葩环境科技有限公司 | Method for manufacturing fireproof flame-retardation wallpaper |
| CN105131438A (en) * | 2015-09-02 | 2015-12-09 | 中国化工集团曙光橡胶工业研究设计院有限公司 | High-thermal-insulation ablation-resistant sizing material |
| CN107629736A (en) * | 2017-09-07 | 2018-01-26 | 滁州市光威化工有限公司 | A kind of nano-silicon dioxide modified fire-retardant the High-speed Cigarette Adhesives for Filter Tipping of hud typed acrylate and vinyl acetate emulsion and preparation method |
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| Title |
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